JP2009501949A - Photopolymer composition suitable for lithographic printing plates - Google Patents

Abstract

｛上記式中X¹、X²、及びX³は独立して、直鎖又は環状C₄〜C₁₂アルキレン及びC₆〜C₁₀アリーレン、複素環基、複素芳香族基、並びに上記のものの2つ又は3つ以上の組合わせから選択され、
R¹、R²、及びR³は独立して、

から選択され、
但し、(1)基R¹、R²、及びR³のうちの少なくとも1つにおいてn＝0であり、そして(2)基R¹、R²、及びR³のうちの少なくとも1つにおいてn＞2であり、そして(3)少なくとも1つの基R⁶が、式(III)中でHとは異なるものとする｝
の少なくとも1種のオリゴマーA
を含む輻射線感光性塗膜と
を含んで成る輻射線感光性要素。(a) a substrate;
(b) (i) at least one component selected from a photoinitiator and a sensitizer / co-initiator system that absorbs radiation in the wavelength range 250-1200 nm;
(ii) Formula (I):

{Wherein X ¹ , X ² and X ³ are independently linear or cyclic C _{4 to} C ₁₂ alkylene and C _{6 to} C ₁₀ arylene, a heterocyclic group, a heteroaromatic group, and 2 of the above. Selected from one or a combination of three or more,
R ¹ , R ² , and R ³ are independently

Selected from
However, (1) groups R ^1, R ^2, and an n = 0 in at least one of R ^3, and (2) the radicals R ^1, R ^2, and n in at least one of R ³ > 2 and (3) at least one group R ⁶ shall be different from H in formula (III)}
At least one oligomer A
A radiation-sensitive element comprising a radiation-sensitive coating film.

Description

  The present invention relates to a radiation-sensitive element, in particular a radiation-sensitive element whose coating comprises an oligomer having a biuret structural unit. The invention further relates to a method for producing the element, a radiation-sensitive composition suitable for the method for producing the element, and a method for producing an imaged element from the radiation-sensitive element.

  Lithographic printing is based on the immiscibility of oil and water. The oily material or printing ink is preferably received by the image area and the water or fountain solution is preferably received by the non-image area. When a properly manufactured surface is wetted with water and the printing ink is applied, the background or non-image area receives water and repels the printing ink, whereas the image area receives printing ink, Play the water. The printing ink in the image area is then transferred to a material to be imaged, such as paper or fabric. In general, however, the printing ink is first transferred to an intermediate material called a blanket, which then transfers the printing ink onto the imaged surface. This technique is called offset lithographic printing.

  A frequently used type of lithographic printing plate precursor comprises a photosensitive coating applied on an aluminum-based substrate. Since the coating can react to radiation, the exposed portion becomes soluble so that it is removed during the development process. Such a version is called a positive type. On the other hand, when the exposed part of the coating is cured by radiation, it is called negative. In both cases, the remaining image areas receive printing ink, i.e. oleophilic, and the non-image areas (background) receive water, i.e. hydrophilic. The distinction between image areas and non-image areas takes place during exposure, during which the film is attached to the printing plate precursor under vacuum in order to ensure good contact. The plate is then exposed to a radiation source. When a positive plate is used, the area on the film corresponding to the image on the plate is opaque so that light does not reach the plate, whereas the area on the film corresponding to the non-image area is It is transparent and allows light to pass through the coating, increasing the solubility of the coating. For negative version, the opposite is done: the area on the film corresponding to the image on the plate is transparent, while the non-image area is opaque. The coating underneath the transparent film area is cured by incident light, whereas areas not affected by light are removed during development. Thus, the photocured surface of the negative plate is oleophilic and accepts printing ink, whereas non-image areas that have been applied with a coating removed by the developer are desensitized. And are therefore hydrophilic.

  Photosensitive mixtures have been used for many years in photopolymerizable compositions for producing photosensitive materials such as soldering masks for printed circuit boards and printing plates. However, for new and advanced applications (eg laser exposure), improved photosensitivity, particularly in the visible spectral range, is required so that the exposure time can be shortened. From an economic point of view, it is also important to be able to use a low intensity laser that is cheaper and more reliable than a high intensity laser. Accordingly, efforts have been made for some time to increase the photosensitivity of the photosensitive mixture to be used in the photopolymerizable composition.

  European Patent Application 0 355 387 describes the following formula:

A photopolymerizable mixture comprising a photoinitiator selected from acrylic acid or alkacrylic acid esters, polymeric binders, photoreducible dyes, trihalogen methyl compounds, and acridine, phenazine and quinoxaline compounds is described. However, the ester leads to the formation of sludge in the developer bath.

  German Patent Application Publication No. 23 61 041, European Patent Application Publication No. 0 582 753, and Japanese Patent Application Laid-Open No. 2001-117217 include a monomer having a urethane group and an ethylenically unsaturated group. A photopolymerizable coating is described. Aged coatings have proven difficult to develop.

  U.S. Pat. Nos. 3,856,830; 4,999,271, and 6,207,347 also describe ethylenically unsaturated urethane monomers. Although photopolymerizable coatings produced with these monomers exhibit good photosensitivity, further improvements are desirable.

  The object of the present invention is to combine improved properties compared to radiation-sensitive elements known to those skilled in the art, in particular high photosensitivity, high thermal stability, and good storage stability. In the case of high resolution and printing plates, it is to provide a new radiation-sensitive element that exhibits a large number of copies on the printing press. Further, during development, no or very little sludge should be formed in the developer bath.

This purpose is
(a) a substrate;
(b) (i) at least one component selected from a photoinitiator and a sensitizer / co-initiator system that absorbs radiation in the wavelength range 250-1200 nm;
(ii) Formula (I):

{Wherein X ¹ , X ² , and X ³ are independently linear or cyclic C ₄ -C ₁₂ alkylene and C ₆ -C ₁₀ arylene, a heterocyclic group, a heteroaromatic group, and 2 of the above. Selected from one or a combination of three or more,
R ¹ , R ² , and R ³ are independently

Selected from
Each R ⁴ is independently selected from a hydrogen atom and CH ₃ , each n is independently 0 or an integer 1-20, and each m is independently 0 or 1;
When n in formula (II) is 0, R ⁵ is independently

Selected from;
When n in formula (II) is an integer from 1 to 20, R ⁵ is independently

Selected from;
And each R ⁶ is independently a hydrogen atom,

Selected from;
However, (1) groups R ^1, R ^2, and an n = 0 in at least one of R ^3, and (2) the radicals R ^1, R ^2, and n in at least one of R ³ > 2 and (3) at least one group R ⁶ shall be different from H in formula (III)}
At least one oligomer A
This is accomplished by providing a radiation sensitive element comprising a radiation sensitive coating comprising:

Unless otherwise specified, the term “alkyl group and alkylene group” used in the present invention means a linear, branched or cyclic alkyl group or alkylene group. These groups optionally include a halogen atom (fluorine, chlorine, bromine, iodine), C ₁ -C ₁₂ alkoxy group,

And one or more substituents selected from —O—R ″, where R ″ is a C _{1 to} C ₁₈ alkyl group.

Unless otherwise specified, the term “aryl group and arylene group” used in the present invention means an aromatic carbocyclic monovalent or divalent group having one or two or more condensed rings. These groups optionally include a halogen atom (fluorine, chlorine, bromine, iodine), C ₁ -C ₁₂ alkoxy group,

And one or more substituents selected from —O—R ″, where R ″ is a C _{1 to} C ₁₈ alkyl group.

Unless otherwise specified, the term `` heterocyclic group '' used in the present invention is a saturated or unsaturated (non-aromatic) ring group, and one or more ring carbon atoms are It means a group substituted with a heteroatom selected from O, S, Se, Te and N, preferably selected from O, S and N, preferably having 1 or 2 carbon atoms. Preferably, the group is a 5 or 6 membered heterocyclic group. Heterocyclic groups can optionally include one or more substituents (bonded to C and / or N atoms). Preferably, the heterocyclic group is unsubstituted or contains one substituent. Optional substituents are preferably selected from halogen atoms, alkyl groups, CN, NO ₂ , NR ^IV ₂ , OR ^IV and SR ^IV (each R ^IV is independently selected from hydrogen and alkyl groups). . Examples of heterocyclic groups include piperidyl, piperazinyl, tetrahydroquinolinyl, pyrrolidyl, tetrahydrofurfuryl, tetrahydropyranyl, morpholinyl and tetrahydrothiophenyl.

Unless otherwise specified, the term “heteroaromatic group” used in the present invention is an aryl group in which one or more ring carbon atoms are O, S, Se, Te and N, preferably Means a group substituted with a heteroatom selected from O, S and N, preferably substituted with 1, 2 or 3 carbon atoms. The heteroaromatic group is optionally selected from a halogen atom, an alkyl group, CN, NR ^IV ₂ , COOR ^IV , OR ^IV and SR ^IV (particularly preferably from an alkyl group, OR ^IV and SR ^IV ) One or more substituents can be included, and each R ^IV is independently selected from hydrogen and alkyl. Substituents can be attached to C and / or N atoms. Examples of heteroaromatic groups are imidazolyl, 1,2,4-triazolyl, pyrazolyl, thiazolyl, pyridyl, quinolinyl, pyrimidyl, 1,3,5-thiadiazolyl, 1,3,5-oxadiazolyl, 1,3,5- Includes triazinyl, benzimidazolyl, acridinyl, furanyl and thienyl.

  The terms “(meth) acrylate” and “(meth) acrylic acid” are meant to mean both “acrylate” and “methacrylate”, as well as both “methacrylic acid” and “acrylic acid”, respectively.

  In order to obtain a high degree of photosensitivity combined with good developability and storage stability, while at the same time preventing the formation of sludge in the processing equipment, the radiation-sensitive composition is a biuret of formula (I). It is important to include at least one type of oligomer.

In the oligomer of formula (I), the groups X ¹ , X ² and X ³ are independently C ₄ -C ₁₂ alkylene groups (preferably C ₄ -C ₈ alkylene groups, particularly preferably hexamethylene), C ₆ -C ₁₀ arylene group (preferably phenylene or naphthylene), a divalent heterocyclic group, divalent heteroaromatic group, and two or more combinations of the foregoing (e.g. alkyl aryl, alkyl arylalkyl, and aryl Heteroaryl and heteroaromatic groups are not preferred. X ¹ = X ² = X ³ is preferred, and X ¹ = X ² = X ³ = hexamethylene is particularly preferred.

R ¹ , R ² , and R ³ are independently

Selected from.

N = 0 in at least one of the groups R ¹ , R ² , and R ³ and n> 2 in at least one; n = 0 in one group and another one group If n> 2, then it is essential to the invention that n in the third group can be 0 or any integer from 1 to 20. Preferably n = 0 in two of the groups R ¹ , R ² and R ³ and n> 2 in the third group.

In the formula (II), when n = 0, R ⁵ is independently —CH═CH ₂ , —CH ₂ —CH═CH ₂ , and

Selected from;
when n is an integer from 1 to 20, R ⁵ is independently

Selected from.

  In formula (II), n is preferably> 2; particularly preferably n ≧ 6.

  In formula (III), n is preferably 0 and m is preferably 0 or 1.

R ⁶ is preferably

Or H, provided that at least one R ⁶ is different from H.

It is preferred that at least one group of R ¹ , R ² and R ³ where n> 2 is represented by formula (II).

In the spacer (CHR ⁴ —CHR ⁴ —O) — it is preferred that both groups R ⁴ represent hydrogen or one represents hydrogen and the other represents CH ₃ . Spacer (CHR ⁴ -CHR ⁴ -O) _n -is, for example, a polyethylene glycol unit, a polypropylene glycol unit, or a block having one or more polypropylene glycol blocks and one or more polyethylene glycol blocks Preferably it can be a copolymer unit.

According to one embodiment, two of the groups R ¹ , R ² and R ³ are glycerol-1,3-di (meth) acrylate groups and the third group is polyethylene glycol (meth). An acrylate group or a polypropylene glycol (meth) acrylate group (each with n> 2, preferably n ≧ 6).

The oligomer A of formula (I) can be prepared as follows:
In the first step, the formula:
O = C = NXN = C = O
(Wherein X is defined as X ¹ , X ² , and X ³ ) and an appropriately selected amount of water, usually 3 moles of diisocyanate and 1 mole of diisocyanate. Basic biuret structures are prepared by reacting with water (for example, German Patent Publication No. 1,101,394 and Houben-Weyl, Methoden der organischen Chemie [method in organic chemistry]], 4th Edition (1963), Volume 14/2, page 69 et seq.). The reaction is preferably carried out without a solvent.

In the second step, so that a compound of formula (I) is obtained (n = 0 in at least one of the groups R ¹ , R ² and R ³ and n> in at least one of these) 2), containing a terminal isocyanate group and one or more hydroxy groups:

(Wherein R ⁴ , R ⁵ , R ⁶ , n and m are as described above)
Are reacted with at least two different unsaturated compounds.

  The reaction can be carried out stepwise (ie, reacting the unsaturated compound with biuret one after the other) or simultaneously (ie, reacting all of the unsaturated compound with biuret at the same time).

  The reaction is usually in the presence of a catalyst (e.g. tertiary amine or organotin compounds such as dibutyltin dilaurate and dioctyltin dilaurate) and an inhibitor to prevent thermal polymerization at temperatures between room temperature and about 80 ° C. It is carried out in an aprotic solvent such as benzene, toluene, xylene, ketone (eg methyl ethyl ketone), or ester (eg butyl acetate).

By appropriately selecting the molar ratio of the unsaturated compound, the ratio of the different groups R ¹ , R ² , and R ³ can be controlled. Details regarding the preparation of the oligomer A can be inferred from, for example, German Offenlegungsschrift 2,361,041.

  The radiation-sensitive coating film can contain one or more oligomers A.

  The amount of oligomer A in the radiation-sensitive layer is not particularly limited, but oligomer A is preferably present in an amount of 10 to 90% by weight based on the dry layer weight (particularly preferably 10 to 70% by weight).

  The radiation-sensitive coating further comprises at least one absorber component selected from photoinitiators and sensitizer / co-initiator systems.

  The absorber component is selected such that significant absorption can be achieved in the range where the radiation source to be used later during imaging emits light, preferably the absorber has an absorption maximum within that range. Indicates. Thus, if the radiation sensitive element is to be imaged by an IR laser, the absorber essentially absorbs radiation in the range of about 750 to 1,200 nm, and preferably in that range. Should show the absorption maximum. On the other hand, if the imaging is to be performed by UV radiation, the absorber essentially absorbs radiation in the range of about 250-400 nm and preferably exhibits an absorption maximum in that range. Should. Suitable photoinitiators and / or sensitizers are known to those skilled in the art, or whether a significant absorption occurs within the expected wavelength range is easily determined by simple tests (e.g. recording absorption spectra). Can be determined.

In the present invention, a photoinitiator is a compound that can absorb radiation upon exposure and can form free radicals by itself, ie without the addition of coinitiators. Examples of suitable photoinitiators are triazine derivatives having 1 to 3 CX ₃ groups, each X being independently selected from a chlorine or bromine atom and preferably a chlorine atom, hexaarylbisimidazole Including compound, benzoin ether, benzyl ketal, oxime ether, oxime ester, α-hydroxy or α-aminoacetophenone, acylphosphine, acylphosphine oxide, acylphosphine sulfide, metallocene, peroxide. Examples of suitable triazine derivatives are 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2- (styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis (trichloro Methyl) -s-triazine and 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis (trichloromethyl) -s-triazine Suitable oxime ethers and oxime esters Are derived, for example, from benzoin Preferred metallocenes are, for example, two 5-membered cyclodienyl groups, for example cyclopentadienyl groups, and at least one And the most preferred metallocene is bis (cyclopentadienyl) -bis- [2] which is an ortho fluorine atom and optionally one or two six-membered aromatic groups also having one pyryl group. , 6-Difluoro-3- (pyrid-1-yl) -phenyl] titanium and dicyclopentadiene-bis-2,4,6-trifluorophenyl-titanium or zirconium.

  In the present invention, a single photoinitiator or a mixture of two or more can be used.

  Photoinitiators can be used alone or in combination with one or more coinitiators, and the addition of coinitiators can increase the effect of photoinitiation.

  The amount of the photoinitiator is not particularly limited, but when a photoinitiator is present, it is preferably 0.2 to 25% by weight, particularly preferably 0.5 to 15% by weight, based on the dry layer weight. .

  The sensitizers referred to in the present invention are compounds that can absorb radiation when exposed to light, but cannot form free radicals by themselves, that is, without the addition of coinitiators.

  All light absorbing compounds that are photooxidizable or photoreducible, or that can transfer their excitation energy to the acceptor molecule are suitable sensitizers for use in the present invention. Examples of such dyes are cyan dyes, merocyanine dyes, oxonol dyes, diarylmethane dyes, triarylmethane dyes, xanthene dyes, coumarin derivatives, ketocoumarin dyes, acridine dyes, phenazine dyes, quinoxaline dyes, pyrylium dyes, or thiapyrylium dyes. Azaannulene dyes (e.g. phthalocyanines and porphyrins), indigo dyes, anthraquinone dyes, polyarylenes, polyarylpolyenes, 2,5-diphenylisobenzofurans, 2,5-diarylfurans, 2,5-diarylthiofurans, 2,5- Didiarylpyrrole, 2,5-diarylcyclopentadiene, polyarylphenylene, polyaryl-2-pyrazoline, carbonyl compounds such as aromatic ketones or quinones such as benzophenone derivatives, Michler's ketone, thioxyl Sandton derivatives, anthraquinone derivatives, and fluorenone derivatives are included.

  For IR-sensitive elements, the sensitizers are for example from carbon black, phthalocyanine pigments / dyes, and polythiophene-squarylium, thiazolium, croconate, merocyanine, cyanine, indolizine, pyrylium, or metal dithioline class pigments / dyes. Particularly preferably selected from the cyanine class. For example, the compounds described in Table 1 of US Pat. No. 6,326,122 are suitable IR absorbers. Further examples are U.S. Pat.Nos. 4,327,169, 4,756,993, 5,156,938, WO 00/29214, U.S. Pat.No. 6,410,207, and EP 1 176. Can be found in the 007 specification.

  According to one embodiment, the formula (IV):

In the above formula,
Each Z ¹ independently represents S, O, NR ^a or C a (alkyl) _2;
Each R ′ independently represents an alkyl group, an alkyl sulfonate group, or an alkyl ammonium group;
R ″ represents a halogen atom, SR ^a , OR ^a , SO ₂ R ^a or NR ^a ₂ ;
Each R ′ ″ independently represents a hydrogen atom, an alkyl group, —COOR ^a , OR ^a , —SR ^a , —NR ^a ₂ , or a halogen atom; R ′ ″ may be a benzo-fused ring; Often;
A ⁻ represents an anion;
R ^b and R ^c both represent a hydrogen atom or together with the carbon atom to which they are attached form a carbocyclic 5 or 6 membered ring;
R ^a represents a hydrogen atom, an alkyl or aryl group;
Each b is independently 0, 1, 2 or 3.

When R ′ represents an alkyl sulfonate group, an inner salt can be formed such that the anion A ⁻ is not required. If R 'represents an alkylammonium group, A ^- same or A ^- it is required different from a second counterion with.
Z ¹ is preferably a C (alkyl) ₂ group;
R ′ is preferably an alkyl group having 1 to 4 carbon atoms;
R ″ is preferably a halogen atom or SR ^a ;
R ′ ″ is preferably a hydrogen atom;
R ^a is preferably an optionally substituted phenyl group, or an optionally substituted heteroaromatic group (e.g. in the case of SR ^a , the sulfur atom can form part of an aromatic ring. ).

Preferably, R ^b and R ^c together with the carbon atom to which they are attached form a carbocyclic 5 or 6 membered ring.

The counter ion A ⁻ is preferably a chloride ion, trifluoromethylsulfonate or tosylate anion.

Of the IR dyes of formula (II),
Particularly preferred are dyes having a symmetrical structure.

Examples of particularly preferred IR absorbers are:
2- [2- [2-Phenylsulfonyl-3- [2- (1,3-dihydro-1,3,3-trimethyl-2H-indole-2-ylidene) -ethylidene] -1-cyclohexen-1-yl ] -Ethenyl] -1,3,3-trimethyl-3H-indolium chloride,
2- [2- [2-thiophenyl-3- [2- (1,3-dihydro-1,3,3-trimethyl-2H-indole-2-ylidene) -ethylidene] -1-cyclohexen-1-yl] -Ethenyl] -1,3,3-trimethyl-3H-indolium chloride,
2- [2- [2-thiophenyl-3- [2- (1,3-dihydro-1,3,3-trimethyl-2H-indole-2-ylidene) -ethylidene] -1-cyclopenten-1-yl] -Ethenyl] -1,3,3-trimethyl-3H-indolium tosylate,
2- [2- [2-Chloro-3- [2- (1,3-dihydro-1,3,3-trimethyl-2H-benzo [e] -indole-2-ylidene) -ethylidene] -1-cyclohexene -1-yl] -ethenyl] -1,3,3-trimethyl-1H-benzo [e] -indolium-tosylate, and
2- [2- [2-Chloro-3- [2-ethyl- (3H-benzthiazol-2-ylidene) -ethylidene] -1-cyclohexen-1-yl] -ethenyl] -3-ethyl-benzthiazolium -Includes tosylate.

  The following compounds are also IR absorbers suitable for the present invention.

  In the present invention, one kind of sensitizer or a mixture of two or more kinds can be used.

  Sensitizers are used in combination with one or more coinitiators. In addition, photoinitiators can be used, but this is not preferred.

  The amount of the sensitizer is not particularly limited, but when a sensitizer is present, the sensitizer is preferably 0.2 to 15% by weight, particularly preferably 0.5 to 10%, based on the dry layer weight. % By weight. When photoinitiators and sensitizers are present in the coating, their total amount is preferably 0.5 to 30% by weight, particularly preferably 1 to 15% by weight, based on the dry layer weight.

Co-initiators referred to in the present invention are compounds that are essentially unable to absorb when exposed to light and form free radicals with a light absorption sensitizer or photoinitiator. Co-initiators suitable for use in the present invention include, for example, amines such as alkanolamines or 4-dialkylaminobenzoates, diaryl iodonium salts, triaryl sulfonium salts, aryl diazonium salts, N-aryl glycine derivatives, diaryl diiminos. Diacetic acid compounds, aryloxyacetic acids, aromatic sulfonyl halides, trihalomethyl sulfones, nitrogen heterocycles with N-oxide substituents (eg alkoxypyridinium salts), nitrogen heterocycles such as N-benzoyl-oxyphthalimide, diazosulfonate , 9,10-dihydro-anthracene derivative, a thiol compound (e.g. mercaptobenzthiazoles, mercaptobenzimidazoles, and mercaptotriazole), even independently triazine derivative (any X with one to three CX ₃ groups, chlorine or A hexaarylbisimidazole compound, benzoin ether, benzyl ketal, oxime ether, oxime ester, α-hydroxy or α-aminoacetophenone, acylphosphine, acylphosphine oxide, acyl Including phosphine sulfides, metallocenes, peroxides, etc., carbonyl compounds such as aromatic ketones or quinones such as benzophenone derivatives, Michler ketones, thioxanthone derivatives, anthraquinone derivatives, and fluorenone derivatives.

  A suitable 2,2 ′, 4,4 ′, 5,5′-hexaarylbiimidazole (hereinafter simply referred to as hexaarylbiimidazole) is represented by the following formula (V):

Represented by
In the above formula, A ^{1 to} A ⁶ are the same or different substituted or unsubstituted C _{5 to} C ₂₀ aryl groups, and one or two or more carbon atoms are arbitrarily selected in the ring of the group Optionally, a group that can be substituted by a heteroatom selected from O, N and S. Suitable substituents are the substituents of preventing light-induced dissociation to triarylimidazolyl radicals for aryl groups, such as halogen atom (fluorine, chlorine, bromine, iodine), - CN, C ₁ ~C ₆ alkyl (optionally comprises a halogen atom, one or two or more substituents selected -CN, and from -OH), C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, (C it is ₁ -C ₆ alkyl) sulfonyl.

  Preferred aryl groups are substituted and unsubstituted phenyl, biphenyl, naphthyl, pyridyl, furyl, and thienyl groups. Particularly preferred are substituted and unsubstituted phenyl groups, and particularly preferred are halogen-substituted phenyl groups.

Examples of these are:
2,2'-bis (bromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2′-bis (p-carboxyphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole,
2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetrakis (p-methoxyphenyl) -biimidazole,
2,2′-bis (p-chlorophenyl) -4,4 ′, 5,5′-tetrakis (p-methoxyphenyl) -biimidazole,
2,2′-bis (p-cyanophenyl) -4,4 ′, 5,5′-tetrakis (p-methoxyphenyl) -biimidazole,
2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (2,4-dimethoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (o-ethoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2′-bis (m-fluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole,
2,2'-bis (o-fluorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (p-fluorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (o-hexoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2′-bis (o-hexylphenyl) -4,4 ′, 5,5′-tetrakis (p-methoxyphenyl) -biimidazole,
2,2'-bis (3,4-methylenedioxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetrakis (m-methoxyphenyl) biimidazole,
2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetrakis [m- (betaphenoxy-ethoxyphenyl)] biimidazole,
2,2'-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (o-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2′-bis (p-methoxyphenyl) -4,4′-bis (o-methoxyphenyl) -5,5′-diphenylbiimidazole,
2,2'-bis (o-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2′-bis (p-phenylsulfonylphenyl) -4,4 ′, 5,5′-tetraphenyl-biimidazole,
2,2'-bis (p-sulfamoylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (2,4,5-trimethylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-di-4-biphenylyl-4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-di-1-naphthyl-4,4 ', 5,5'-tetrakis (p-methoxyphenyl) -biimidazole,
2,2'-di-9-phenanthryl-4,4 ', 5,5'-tetrakis (p-methoxyphenyl) -biimidazole,
2,2′-diphenyl-4,4 ′, 5,5′-tetra-4-biphenylylbiimidazole,
2,2'-diphenyl-4,4 ', 5,5'-tetra-2,4-xylylbiimidazole,
2,2'-di-3-pyridyl-4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-di-3-thienyl-4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-di-o-tolyl-4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-di-p-tolyl-4,4'-di-o-tolyl-5,5'-diphenylbiimidazole,
2,2'-di-2,4-xylyl-4,4 ', 5,5'-tetraphenylbiimidazole,
2,2 ', 4,4', 5,5'-hexakis (p-phenylthiophenyl) biimidazole,
2,2 ', 4,4', 5,5'-hexa-1-naphthylbiimidazole,
2,2 ', 4,4', 5,5'-hexaphenylbiimidazole,
2,2'-bis (2-nitro-5-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, and
2,2'-bis (o-nitrophenyl) -4,4 ', 5,5'-tetrakis (m-methoxyphenyl) biimidazole,
2,2'-bis (2-chloro-5-sulfophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
Including

And especially preferred are:
2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-fluorophenyl) biimidazole,
2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (p-iodophenyl) biimidazole,
2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-chloronaphthyl) biimidazole,
2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-chlorophenyl) biimidazole,
2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (p-chloro-p-methoxyphenyl) biimidazole,
2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole,
2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (o, p-dibromophenyl) biimidazole,
2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole, or
2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole; but the invention is limited to these compounds It is not a thing.

  Suitable hexaarylbiimidazoles can be prepared according to well-known methods (see, eg, US Pat. No. 3,445,232). A preferred process is the oxidative dimerization of the corresponding triarylimidazole with iron- (II) -hexacyanoferrate (II) in an alkaline solution.

  Use hexaarylbiimidazole isomers (or a mixture of isomers) (e.g. 1,2'-, 1,1'-, 1,4'-, 2,2'-, 2,4'-, and 4 , 4'-isomer) is unsuitable for the purposes of the present invention as long as it is photolabile and provides a triarylimidazolyl radical in the process.

Trihalogen methyl compounds suitable as coinitiators can form free radicals. Trihalogenmethyl substituted triazines and trihalogenmethyl-aryl sulfones are preferred. The following can be mentioned by way of example (the invention is not limited to these compounds):
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine,
2- (4-chlorophenyl) -4,6-bis- (trichloromethyl) -s-triazine,
2-phenyl-4,6-bis (trichloromethyl) -s-triazine,
2,4,6-tri- (trichloromethyl) -s-triazine,
2,4,6-tri- (tribromomethyl) -s-triazine and tribromomethylphenylsulfone.

  Many coinitiators can also function as photoinitiators when exposed in the absorption band. Thus, for example, photoinitiators or sensitizers span the long wavelength spectral range (IR and / or visible range) and co-initiators span the short wavelength spectral range (eg UV range), so that a wide spectral range. A photosensitive layer that is photosensitive over a wide range can be obtained. This effect can be advantageous if the consumer wants to irradiate the same material with different sources of radiation. In this case, the coinitiator functions as an actual coinitiator in the sense of the above definition for the IR or visible range, whereas it functions as a photoinitiator for the UV range.

  In the present invention, a coinitiator or a mixture of coinitiators can be used.

  The amount of coinitiator is not specifically limited, but is preferably 0.2 to 25% by weight, particularly preferably 0.5 to 15% by weight, based on the dry layer weight.

  In addition to the radically polymerizable oligomer A, the radiation-sensitive coating film can also contain other C—C unsaturated monomers and / or oligomers and / or polymers containing at least one C—C double or triple bond. Such compounds are well known to those skilled in the art and can be used in the present invention without any specific limitations. Preference is given to esters of acrylic acid and methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and fumaric acid having one or more unsaturated groups in the form of monomers, oligomers or prepolymers. These may exist in solid or liquid form, with solid and highly viscous forms being preferred. Suitable compounds as monomers are, for example, trimethylolpropane triacrylate and trimethacrylate, pentaerythritol triacrylate and trimethacrylate, dipentaerythritol monohydroxypentaacrylate and pentamethacrylate, dipentaerythritol hexaacrylate and hexamethacrylate, pentaerythritol tetraacrylate and Tetramethacrylate, ditrimethylolpropane tetraacrylate and tetramethacrylate, diethylene glycol diacrylate and dimethacrylate, triethylene glycol diacrylate and dimethacrylate, or tetraethylene glycol diacrylate and dimethacrylate. Suitable oligomers and / or prepolymers include, for example, urethane acrylates and methacrylates, epoxide acrylates and methacrylates, polyester acrylates and methacrylates, polyether acrylates and methacrylates, or unsaturated polyester resins.

  In addition to the monomer and / or oligomer, a polymer containing a radically polymerizable C—C double bond in the main chain or side chain can also be used. Examples include reaction products of maleic anhydride olefin copolymers and hydroxyalkyl (meth) acrylates; polyesters containing allyl alcohol ester groups; reaction products of polymeric polyalcohols and isocyanato (meth) acrylates; Polyesters; polystyrenes terminated with (meth) acrylates, poly (meth) acrylic esters, poly (meth) acrylic acids, poly (meth) acrylamides, and polyethers can be used. In this context, the prefix “(meth)” indicates that both acrylic and methacrylic acid derivatives can be used.

  Additional suitable C—C unsaturated radically polymerizable compounds are described, for example, in EP 1 176 007.

  The radically polymerizable monomer, oligomer or polymer different from the oligomer A is preferably present in an amount of 0 to 40% by weight based on the dry layer weight of the radiation-sensitive coating film, and the monomer / oligomer is used. If present, they are particularly preferably present in an amount of 0 to 20% by weight.

  Optionally, the radiation-sensitive coating can also include a binder or binder mixture. The binder is preferably selected from polyvinyl acetals, acrylic polymers, and polyurethanes. It is preferred that the binder contains an acid group, particularly preferably a carboxy group. Most preferred is an acrylic polymer. The binder having acid groups preferably has an acid value of 20 to 180 mg KOH per gram of polymer. Optionally, the binder can include unsaturated groups in the main chain or side chain. Such unsaturated bonds can be subjected to radical photopolymerization reactions or other photoreactions such as 2 + 2-photocycloaddition.

  The binder is preferably present in an amount of 0 to 90% by weight, particularly preferably 10 to 60% by weight, based on the dry layer weight.

  In order to prevent undesired thermal polymerization of the ethylenically unsaturated monomer during formation or storage of the photosensitive composition, the radiation sensitive coating optionally includes a small amount of thermal polymerization inhibitor. It can also be included. Suitable examples of thermal polymerization inhibitors include, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thio-bis- (3- Methyl-6-t-butylphenol), 2,2′-methylene-bis- (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxylamine salts. The amount of the polymerization inhibitor in the photosensitive composition of the present invention is preferably 0 to 5% by weight, particularly preferably 0.01 to 2% by weight, based on the dry layer weight. Such thermal polymerization inhibitors are often introduced into the radiation-sensitive coatings via commercial monomers or oligomers and are therefore not specifically mentioned.

  Furthermore, the radiation-sensitive coating film of the present invention can contain a dye or pigment for coloring the layer. Examples of colorants include, for example, phthalocyanine pigments, azo pigments, carbon black and titanium dioxide, ethyl violet, crystal violet, azo dyes, anthraquinone dyes and cyanine dyes. The amount of the colorant is preferably 0 to 20% by weight, particularly preferably 0.5 to 10% by weight, based on the weight of the dry layer.

  In order to improve the physical properties of the cured layer, the radiation-sensitive coatings according to the invention can additionally contain further additives, such as plasticizers or inorganic fillers. Suitable plasticizers include, for example, dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and tricresyl phosphate. The amount of the plasticizer is not particularly limited, but is preferably 0 to 10% by weight, particularly preferably 0.25 to 5% by weight, based on the weight of the dry layer.

  The radiation-sensitive coating film can also contain a known chain transfer agent such as a mercapto compound. The chain transfer agent is preferably used in an amount of 0 to 15% by weight, particularly preferably 0.5 to 5% by weight, based on the dry layer weight.

  In addition, the radiation-sensitive coating can include leuco dyes such as leuco crystal violet and leuco malachite green. These leuco dyes are preferably present at 0 to 10% by weight, particularly preferably 0.5 to 5% by weight, based on the dry layer weight.

  In addition, the radiation-sensitive coating film can contain a surfactant. Suitable surfactants include siloxane-containing polymers, fluorine-containing polymers, and polymers having ethylene oxide and / or propylene oxide groups. These surfactants are preferably present in an amount of 0 to 10% by weight, particularly preferably 0.2 to 5% by weight, based on the dry layer weight.

Other optional components of the radiation-sensitive coating are inorganic fillers such as Al ₂ O ₃ and SiO ₂ . The inorganic filler is preferably present in an amount of 0 to 20% by weight, particularly preferably 0.1 to 5% by weight, based on the dry layer weight.

  The radiation-sensitive element according to the present invention may be, for example, a printing plate precursor (specifically, a lithographic printing plate precursor), an integrated circuit substrate, or a photomask.

  In producing the printing form precursor, a plate-like or foil-like material having dimensional stability is preferably used. Preferably, a plate-like or foil-like material having dimensional stability already used as a substrate for printed matter is used. Examples of such substrates are paper, paper coated with plastic materials (e.g. polyethylene, polypropylene, polystyrene), metal plates or foils, e.g. aluminum (including aluminum alloys), zinc and copper plates, e.g. cellulose diacetate, Cellulose triacetate, cellulose propionate, cellulose acetate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, plastic film formed from polyethylene, polystyrene, polypropylene, polycarbonate and polyvinyl acetate, and paper or plastic film as described above Includes laminate material formed from one of the metals, or paper / plastic film metallized by vapor deposition. Of these substrates, aluminum plates or foils are particularly preferred. This is because an aluminum plate or foil exhibits excellent dimensional stability, is inexpensive, and also exhibits excellent adhesion to the coating. In addition, a composite film can be used, in which an aluminum foil is laminated onto a polyethylene terephthalate film.

  For metal substrates, in particular aluminum substrates, a graining treatment (for example by brushing in a dry state or by brushing with a polishing suspension or by electrochemical graining with eg a hydrochloric acid electrolyte), anode It is preferable that at least one treatment selected from a treatment and a hydrophilization treatment is performed.

Sodium silicate, calcium zirconium fluoride, polyvinylphosphonic acid or phosphoric acid to improve the hydrophilic properties of the surface of metal substrates, optionally grained and optionally anodized in sulfuric acid or phosphoric acid A post-treatment with an aqueous solution can be applied to the metal substrate. Within the scope of the present invention, the term “substrate” also encompasses an optionally pretreated substrate, for example showing a hydrophilizing layer on its surface.
Details of the substrate pretreatment described above are known to those skilled in the art.

  In order to produce a radiation-sensitive element, the radiation-sensitive composition of the present invention can be applied to a hydrophilic surface of a substrate by a common application process (e.g., spin coating, spray coating, dip coating, doctor blade coating). Applies to Although it is possible to apply a radiation-sensitive composition to both sides of the substrate, for the elements of the present invention, it is preferred that the radiation-sensitive coating is applied to one side of the substrate.

Usually, the radiation-sensitive composition is applied from an organic solvent or solvent mixture.
Suitable solvents are lower alcohols (eg methanol, ethanol, propanol and butanol), glycol ether derivatives (eg ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate) , Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether), ketones (e.g. diacetone alcohol, acetylacetone, Seton, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone), esters (e.g. methyl lactate, ethyl lactate, ethyl acetate, 3-methoxypropyl acetate and butyl acetate), aromatics (e.g. toluene and xylene), cyclohexane, 3-methoxy-2- Propanol, 1-methoxy-2-propanol, methoxymethoxyethanol, γ-butyrolactone, and dipolar aprotic solvents (eg, THF, dimethyl sulfoxide, dimethylformamide, and N-methylpropyrolidone), and mixtures thereof. The solids content of the radiation-sensitive mixture to be applied depends on the coating method used and is preferably 1 to 50% by weight.

The dry layer weight of the radiation-sensitive layer is preferably 0.5 to 4 g / m ² , more preferably 0.8 to 3 g / m ² .

It may be advantageous to additionally apply a water-soluble oxygen-impermeable overcoat layer on the radiation-sensitive layer. Suitable polymers for such overcoat layers include, among others, polyvinyl alcohol, polyvinyl alcohol / polyvinyl acetate copolymers, polyvinyl pyrrolidone, polyvinyl pyrrolidone / polyvinyl acetate copolymers, and gelatin. The layer weight of the topcoat layer may be, for example, 0.1 to 6 g / m ² , preferably 0.5 to 4 g / m ² . However, the printing plate precursor according to the present invention exhibits excellent properties even without an overcoat layer. The overcoat layer can also include a matting agent (ie, organic or inorganic particles having a particle size of 2-20 μm) that facilitates planar positioning of the film during contact exposure.

  The printing plate precursor thus produced is subjected to imagewise exposure with radiation of a suitable wavelength in a manner known to those skilled in the art, followed by development with a commercially available aqueous alkaline developer. To do. After imagewise exposure (ie, before development), heat treatment can be performed at 50 to 180 ° C, preferably 90 to 150 ° C.

  The developed element can be treated with preservatives ("gamming") using common methods. Preservatives are aqueous solutions of hydrophilic polymers, wetting agents, and other additives.

  For certain applications, it is further advantageous to increase the mechanical strength of the printed layer by subjecting it to a heat treatment (referred to as “baking”) and / or an overall exposure (eg UV light). For this purpose, prior to processing, the plate is treated with a solution that protects the non-image areas, so that the heat treatment does not cause these areas to accept ink. Suitable solvents for this purpose are described, for example, in US Pat. No. 4,355,096. Baking is usually performed at a temperature of 150 to 250 ° C. However, printing plates prepared from printing plate precursors according to the present invention exhibit excellent properties even without heat treatment / overall exposure. If both baking and overall exposure are performed, the two processing steps can be performed simultaneously or in succession.

  The lithographic printing plate precursor according to the present invention is characterized by improved photosensitivity combined with good storage stability, and the improved printing plate has excellent wear resistance allowing many copies Indicates.

  Within the scope of the present invention, the term “radiation-sensitive element” also includes elements in which the substrate comprises a radiation-sensitive coating (and optionally an oxygen-impermeable overcoat layer) on both sides. However, single-sided coatings are preferred.

The invention is explained in more detail in the following examples.
The following abbreviations are used as follows:
Desmodur ™ 100 trifunctional isocyanate (hexuremethylene diisocyanate biuret), available from Bayer,
HMDI hexamethylene diisocyanate
GDMA Glycerol-1,3-dimethacrylate (n = 0 in formula IIIa)
HEMA (2-hydroxyethyl) methacrylate (n = 1 in formula IIa)
PPGMA Polypropylene glycol methacrylate (n = 6 in formula IIa)
PEGMA Polyethylene glycol methacrylate (n = 10 in formula IIa)
HEPi 2- (2-hydroxyethyl) -piperidine
HEA (2-hydroxyethyl) acrylate (n = 1 in formula IIa)
PETA Pentaerythritol triacrylate
DEMA Diethylene glycol methacrylate (n = 2 in formula IIa)

Preparation of monomers 1 to 4 and comparative monomers 1 to 11 Dissolving the corresponding diisocyanate, dibutyltin dilaurate catalyst, stabilizer 2,6-di-tertbutyl-4-methylphenol in methyl ethyl ketone at 40 ° C .; The amount of methyl ethyl ketone was selected so that the final concentration was about 30% by weight. The diisocyanate reaction partner was then added so that the temperature did not exceed 42 ° C. After 2 hours of stirring, the temperature was raised to 60 ° C. and maintained for another 2 hours. The reaction was monitored by IR spectroscopy and finally no isocyanate could be detected. Next, formation of monomers m1 to m4 and comparative monomers cm1 to cm11 was confirmed by GPC.

  The starting compounds, their amounts, the solids content of the reaction mixture, and the resulting product double bond amounts can be obtained from Table 1.

Examples 1-20 and Comparative Examples 1-19
The aluminum foil that has been subjected to electrochemical graining and anodization is treated with an aqueous solution of polyvinylphosphonic acid (PVPA). The pretreated substrate was coated with the filtered solution shown in Table 2 or 3, which was then dried at 90 ° C. for 4 minutes. The dry layer weight of the photopolymer layer was about 1.7 g / m ² in each case.

3)

An overcoat layer was applied to the resulting sample by applying an aqueous solution of poly (vinyl alcohol) (Celvol 203 available from Airproducts; degree of hydrolysis: 88%). After drying at 90 ° C. for 4 minutes, a printing plate precursor having a dry weight of the overcoat layer of about 2.5 g / m ² was obtained.

  A printing plate prepared with a composition according to Table 2, which is sensitive to 405 nm, was subjected to imagewise exposure with a Lithotech imagesetter Andromeda (30 mW, 405 nm UV laser diode) (UGRA / FOGRA Postscript A strip, version 2.0 ERS was used for this purpose), which was then immediately heated in an oven at 90 ° C. for 2 minutes. The printing plate was then developed with developer D1 in Table 4.

For printing plates prepared with the composition according to Table 3 imagewise exposure with Creo imagesetter Trendsetter 3244 (40-90 mJ / cm ² , 830 nm laser diode) and for evaluating the quality of the copy A UGRA / FOGRA Postscript test strip, version 2.0 ERS containing different elements was used. Immediately after exposure, the printing plate was heated in an oven at 90 ° C. for 2 minutes. Subsequently, developer D2 in Table 4 was used for development.

  In all exposed and then heated plates, the overcoat layer was first removed with water and then the respective developer was dispensed onto the plate. After a 30 second dwell time, the plate was rubbed with a tampon for an additional 30 seconds and then the entire plate was rinsed with water. After this treatment, the exposed part remained on the plate. For evaluation of the photosensitivity, the plate was blackened with printing ink in the wet state.

  In preparing a lithographic printing plate, a printing layer is applied to an aluminum foil as described above, which is exposed, heated, developed, rinsed with water, and the developed plate is then subjected to phosphoric acid. Of 0.5% aqueous solution and 6% gum arabic. The plate thus prepared was placed in a sheet-fed offset press and used to print with abrasive printing ink (Offset S7184 available from Sun Chemical, containing 10% potassium carbonate). The background area was tested for possible ink acceptance.

  In order to determine how the monomer (I) affects the properties of the lithographic printing plate, the following test was conducted.

The developable unexposed 5 cm × 30 cm plate strip was heated in an oven at 90 ° C. for 2 minutes to wash off the topcoat layer and dry the strip. The strips were gradually dipped into each developer so that 4 cm was immersed in the developer bath every 5 seconds. After a total residence time of 50 seconds, the strip was removed from the developer bath and the development time was measured as the time required to completely remove the coating. Results can be obtained from Tables 5 and 6.

Photosensitivity
(1) Plate having photosensitivity to 830 nm Photosensitivity was measured using various energy values. The photosensitivity of a given plate was defined as the energy required to obtain a clean image of all microelements of the UGRA / FOGRA Postscript strip, version 2.0 ERS. Both fresh and timed plates (thermal aging: 16 hours at 60 ° C.) were tested. The result can be obtained from Table 5.

(2) Plate having photosensitivity to 405 nm The photosensitivity of this type of plate was measured by performing overall exposure in the above exposure unit. Photosensitivity was defined as the energy required to obtain the two steps of the UGRA gray scale. Both fresh and timed plates (thermal aging: 1 hour at 90 ° C.) were tested. The result can be obtained from Table 6.

Sludge formation in developer bath The following method was used to evaluate sludge formation.
Preheat the plate (110 ° C measured on the back of the plate), wash off the topcoat layer with tap water, develop the plate at 23 ° C for 20 seconds using two brushes, rinse the plate with tap water, and Glunz &Jensen's Raptor Polymer HW type processor, which can be used to gaming the plate with Kodak Polychrome Graphics Gaming Solution 850 S, was loaded with the respective developer (see Table 4). Each plate was exposed with a 5% screen, preheated, and the topcoat was washed off before the plate was immersed in the developer. After a predetermined plate of 15 m ² per liter of developer was developed, the developer bath was emptied. The processor bath of the processor was then tested for residual sludge and, if applicable, sludge removal potential was subsequently evaluated.

The following rating scale was used:
(A) No or little sludge formation,
(B) There is sludge formation; it can be easily removed by rinsing with tap water,
(C) There is sludge formation; it can be removed only after rinsing with tap water for a long time,
(D) There was sludge formation; it could not be removed by rinsing with tap water, necessitating the use of cleanser, dipropylene glycol monomethyl ether.
Results can be obtained from Tables 5 and 6.

Dot Loss The term “dot loss” refers to the change in linearized tone value (TV) during printing. Linearization means that a predetermined set tone value (STV) deviation is compensated by RIP software (RIP = raster image processor). Accessible measurements are the tone values before printing (TVB) and after printing (TVA) on the printing form. In order to measure dot loss, the linearized tone value (TVB) before printing is measured. The linearized and developed printing plate described in the present invention is used in a printing press for 10,000 copies, cleaned, and then subjected again to a tone value test, which is a post-print tone value. (TVA). Dot loss is calculated using equation (1), which integrates all predetermined set tone values (STV).

  In the ideal case, the dot loss converges towards zero. In other words, the lower the dot loss, the better the plate.

  The plates of comparative examples 1 and 11 are used as a reference, i.e. plates with considerable dot loss during printing at different tone values. The relative dot loss is given by equation (2) below:

Calculated using
Results can be obtained from Tables 5 and 6.

This test is used to test whether the layer loss developer due to the developer causes undesirable loss of coating material in the image area. For this purpose, an exposed plate of size 1 dm ² (see Tables 5 and 6 for applied exposure energy) is placed in a 130 mm diameter bowl with the application side up and at 25 ° C. Coated with 50 ml developer.

  After 5 minutes, the sample was removed from the developer and dried at 90 ° C. for 5 minutes. The layer loss due to the developer was measured as follows.

  The lower the layer loss, the better the plate. The results are shown in Table 5.

Adhesion test This test was performed to simulate wear on the printing press. For both plate types, the plates were exposed and preheated as described above. The 10 cm × 20 cm strip was then placed in a water bath at 60 ° C. for 15 minutes and then quickly air dried. The sample was then dried in an oven at 60 ° C. for 4 minutes. After cooling to room temperature, a Tesa ™ adhesive tape strip was applied to a portion of the coating, and a 5 kg cylinder was rolled over the plate to ensure optimal adhesion of the adhesive tape .

  The adhesive tape was then peeled evenly and the optical density of the part without the adhesive tape was compared with the optical density of the part with the adhesive tape. The smaller the difference between the two optical density values, the better the plate.

The following rating scale was used:
+++ There is no difference in optical density and no pinhole is visible even under a microscope;
++ There is no difference in optical density and a few pinholes can be seen under the microscope;
+ There is no difference in optical density and many pinholes can be seen with the naked eye; acceptable
-Total loss of optical density. Optical density loss can be measured with a densitometer, but difficult to identify with the naked eye; unacceptable
-Total loss of optical density. Loss is visible to the naked eye; unacceptable results can be obtained from Tables 5 and 6.

Tacky tackiness is another problem that can occur in photopolymer plates. It is difficult to produce such a plate on a large scale. This is because the roller contacts the photopolymer surface during manufacture. Therefore, it is desirable to keep the tack as low as possible. The tack was tested by first pressing a pre-degreased thumb against the plate and then pressing again the thumb covered with laboratory rubber gloves.

The following rating scale was used:
(1) Excellent; no stickiness is observed with or without gloves;
(2) Good; a slight stickiness is found when gloves are used, and there is no stickiness when using bare thumbs;
(3) Acceptable; slightly sticky with or without gloves;
(4) Unacceptable; considerably sticky when using gloves, and little or no tack when not using gloves;
(6) Unacceptable; considerable stickiness with or without gloves.

  Results can be obtained from Tables 5 and 6.

  Comparing these results, it is clear that only by using the monomers m1 to m4 according to the present invention, sludge formation is insignificant even at high loads, and the comparison monomers cm1 to Compared to the use of cm10, improved developability, improved thermal stability, and higher photosensitivity were found. The number of copies obtained during printing was not affected by the monomers m1 to m4.

Claims (22)

(a) a substrate;
(b) (i) at least one component selected from a photoinitiator and a sensitizer / co-initiator system that absorbs radiation in the wavelength range 250-1200 nm;
(ii) Formula (I):

{Wherein X ¹ , X ² and X ³ are independently linear or cyclic C _{4 to} C ₁₂ alkylene and C _{6 to} C ₁₀ arylene, a heterocyclic group, a heteroaromatic group, and 2 of the above. Selected from one or a combination of three or more,
R ¹ , R ² , and R ³ are independently

Selected from
Each R ⁴ is independently selected from a hydrogen atom and CH ₃ , each n is independently 0 or an integer 1-20, and each m is independently 0 or 1;
When n in formula (II) is 0, R ⁵ is independently

Selected from;
When n in formula (II) is an integer from 1 to 20, R ⁵ is independently

Selected from;
And each R ⁶ is independently a hydrogen atom,

Selected from;
However, (1) groups R ^1, R ^2, and an n = 0 in at least one of R ^3, and (2) the radicals R ^1, R ^2, and n in at least one of R ³ > 2 and (3) at least one group R ⁶ shall be different from H in formula (III)}
At least one oligomer A
A radiation-sensitive element comprising a radiation-sensitive coating film.   The radiation-sensitive coating film further comprises at least one component selected from a binder, a thermal polymerization inhibitor, a colorant, a plasticizer, a chain transfer agent, a leuco dye, an inorganic filler, and a surfactant. Item 2. The radiation-sensitive element according to Item 1. The radiation-sensitive element according to claim 1, wherein X ¹ = X ² = X ³ . Radiation-sensitive element according to ^{X 1 = X 2 = X 3} = 3. hexamethylene. Radiation according to any one of claims 1 to 4, wherein in two of the groups R ¹ , R ² and R ³ n = 0 and in the third group n> 2. Photosensitive element.   6. The radiation-sensitive element according to claim 5, wherein n ≧ 6 in the third group. At least one group, the radiation-sensitive element according to any one of claims 1 to 6 having the formula (II) of R ^1, R ^2, and R ³ is n> 2. R ⁶ in formula (III) is

Or a radiation-sensitive element according to claim 1, wherein at least one group R ⁶ is different from H.   The oligomer A is a reaction product of hexamethylene diisocyanate biuret, glycerin-1,3-di (meth) acrylate, and polypropylene glycol (meth) acrylate, or polyethylene glycol (meth) acrylate. A radiation-sensitive element according to claim 1.   The radiation-sensitive element according to claim 1, wherein the coating film is sensitive to wavelengths in the range of 300 to 410 nm.   The radiation-sensitive element according to claim 1, wherein the coating film is sensitive to wavelengths in the range of 750 to 1,100 nm.   12. The radiation-sensitive element according to claim 1, wherein an oxygen-impermeable overcoat layer is provided on the radiation-sensitive coating film.   The radiation-sensitive element according to any one of claims 1 to 12, wherein the substrate is an aluminum foil or an aluminum plate.   14. The radiation-sensitive element according to any one of claims 1 to 13, wherein the substrate has been subjected to at least one treatment selected from a graining treatment, an anodizing treatment, and a hydrophilizing treatment. (a) to the element according to any one of claims 1 to 14, to a radiation having a wavelength adjusted according to the photoinitiator or sensitizer present in the radiation-sensitive layer of the element; Imagewise exposure; and
(b) A method of producing an imaged element comprising removing unexposed areas with an aqueous alkaline developer.   16. The method of claim 15, wherein the imagewise exposed element obtained in step (a) is heated prior to step (b).   17. A method according to claim 15 or 16, wherein the imaged element obtained in step (b) is heated and / or subjected to overall exposure. (i) at least one component selected from a photoinitiator and a sensitizer / co-initiator system that absorbs radiation in the wavelength range 250-1200 nm;
(ii) Formula (I):

{Wherein X ¹ , X ² , and X ³ are independently linear or cyclic C ₄ -C ₁₂ alkylene and C ₆ -C ₁₀ arylene, a heterocyclic group, a heteroaromatic group, and 2 of the above. Selected from one or a combination of three or more,
R ¹ , R ² , and R ³ are independently

Selected from
Each R ⁴ is independently selected from a hydrogen atom and CH ₃ , each n is independently 0 or an integer 1-20, and each m is independently 0 or 1;
When n in formula (II) is 0, R ⁵ is independently

Selected from;
When n in formula (II) is an integer from 1 to 20, R ⁵ is independently

Selected from;
And each R ⁶ is independently a hydrogen atom,

Selected from;
However, (1) groups R ^1, R ^2, and an n = 0 in at least one of R ^3, and (2) the radicals R ^1, R ^2, and n in at least one of R ³ > 2 and (3) at least one group R ⁶ shall be different from H in formula (III)}
At least one oligomer A; and
(iii) A radiation-sensitive composition comprising a solvent or solvent mixture.   19. The radiation of claim 18, further comprising at least one additional component selected from a binder, a thermal polymerization inhibitor, a colorant, a plasticizer, a chain transfer agent, a leuco dye, an inorganic filler, and a surfactant. A linear photosensitive composition.   20. Use of the radiation-sensitive composition according to claim 18 or 19 for the production of a radiation-sensitive element. (a) preparing a pretreated or untreated substrate;
(b) applying the radiation-sensitive composition according to claim 18 or 19; and
15. The method for producing a radiation-sensitive element according to any one of claims 1 to 14, comprising (c) drying.   The method according to claim 21, wherein after step (c), an oxygen-impermeable overcoat layer is applied.